Mono azo dyes containing as diazo radical a thiophene radical which possesses an oxime group

ABSTRACT

A thiophene-containing azo dye of the formula ##STR1## where R is substituted or unsubstituted alkyl, alkenyl, cycloalkyl or phenyl, X is hydrogen, halogen, hydroxyl, unsubstituted or substituted alkoxy, cycloalkoxy, phenoxy, mercapto, alkylthio, phenylthio, alkylsulfonyl, phenylsulfonyl or phenyl and Y is cyano, nitro, alkanoyl, substituted or unsubstituted benzoyl, alkylsulfonyl, phenylsulfonyl, Co-Z, where Z is unsubstituted or substituted phenoxy, amino, mono- or dialkyl-amino, pyrrolidino, piperidino, morpholino or N-alkyl-piperazino, and K is the radical of a coupling component is used as dyes for dyeing fiber material.

The present invention relates to a novel thiophene-containing azo dyewhose diazo component is a thiophene which has an oxime ether group inthe 4-position on the thiophene ring, and to the use thereof for dyeingfiber material.

DE-A-3,517,365 discloses azo dyes whose diazo component derives from2-aminothiophene derivatives.

It is an object of the present invention to provide a novel thiopheneazo dye which has advantageous application properties.

We have found that this object is achieved with a thiophene-containingazo dye of the formula I ##STR2## in which R is substituted orunsubstituted C₁ -C₁₂ -alkyl, substituted or unsubstituted C₃ -C₆-alkenyl, substituted or unsubstituted C₅ -C₇ -cycloalkyl or substitutedor unsubstituted phenyl, X is hydrogen, halogen, hydroxyl, unsubstitutedor phenyl-substituted C₁ -C₈ -alkoxy, C₅ -C₇ -cycloalkoxy, substitutedor unsubstituted phenoxy, mercapto, unsubstituted or hydroxyl-, C₁ -C₄-alkoxycarbonyl- or phenyl-substituted C₁ -C₈ -alkylthio, C₅ -C₇-cycloalkylthio, substituted or unsubstituted phenylthio, C₁ -C₄-alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, C₁ -C₈-alkyl or substituted or unsubstituted phenyl, Y is cyano, nitro, C₁-C₁₀ -alkanoyl, substituted or unsubstituted benzoyl, C₁ -C₄-alkylsulfonyl, substituted or unsubstituted phenylsulfonyl or CO--Zwhere Z is hydroxyl, unsubstituted or hydroxyl- or C₁ -C₄-alkoxy-substituted C₁ -C₈ -alkoxy, substituted or unsubstitutedphenoxy, amino, C₁ -C₈ -mono- or dialkylamino, pyrrolidino, piperidino,morpholino or N-(C₁ -C₄ -alkyl)piperazino and K is the radical of acoupling component.

Any alkyl or alkenyl group appearing in the above radicals can bestraight-chain or branched.

In any substituted phenyl appearing in the abovementioned formula I, thesubstituents can be, unless otherwise stated, halogen, in particularfluorine, chlorine or bromine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

Possible substituents in R are chlorine, bromine, C₁ -C₄ -alkoxy,substituted or unsubstituted phenyl or phenoxy. Specific examples of Rare: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₇ H₁₅, C₈ H₁₇, C₉ H₁₉,C₁₀ H₂₁, C₁₁ H₂₃, C₁₂ H₂₅, C₂ H₄ Cl, C₂ H₄ OCH₃, C₂ H₄ OC₆ H₅, CH₂CH═CH₂, CH₂ CH═CHCl, CH₂ C₆ H₅, CH₂ C₆ H₄ CH₃, CH₂ C₆ H₄ Cl, CH₂ C₆ H₄OCH₃, C₂ H₄ C₆ H₅, cyclopentyl, cyclohexyl, cycloheptyl, C₆ H₅ or C₆ H₄CH₃.

X is for example: hydrogen, fluorine, chlorine, bromine, OH, OCH₃, OC₂H₅, OC₃ H₇, OC₄ H₉, OC₅ H₁₁, OC₆ H₁₃, OC₇ H₁₅, OC₈ H₁₇, OC₅ H₉, OC₆ H₁₁,OC₇ H₁₃, OCH₂ C₆ H₅, OC₂ H₄ C₆ H₅, OC₆ H₅, OC₆ H₄ CH₃, OC₆ H₄ Cl, SH,SCH₃, SC₂ H₅, SC₃ H₇, SC₄ H₉, SC₅ H₁₁, SC₆ H₁₃, SC₇ H₁₅, SC₈ H₁₇, SC₂ H₄OH, SCH₂ COOCH₃, SCH₂ COOC₂ H₅, SC₆ H₁₁, SCH₂ C₆ H₅, SC₆ H₅, SC₆ H₄ CH₃,CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO.sub. 2, Cl-C₆ H₄ SO₂, C₄ H₉ -C₆H₄ SO₂, CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₇ H₁₅, C₈ H₁₇, C₆ H₅,CH₃ C₆ H₄ or CH₃ OC₆ H₄.

Y can be for example in addition to those already mentioned: ##STR3##

In the formula I, K is the radical of a coupling component. Thesecomponents conform to the formula KH and come from the aniline,naphthylamine, pyrazolone, aminopyrazole, indole, thiazole, thiophene,tetrahydroquinoline or pyridine series.

They conform in particular to the general formulae II to X: ##STR4##

In these formulae, B¹ is hydrogen or B², B² is substituted orunsubstituted C₁ -C₈ -alkyl, substituted or unsubstituted C₅ -C₇-cycloalkyl, substituted or unsubstituted phenyl, C₃ -C₆ -alkenyl oracyl, T¹ is hydrogen, unsubstituted or phenyl-substituted C₁ -C₄ -alkylor substituted or unsubstituted phenyl, T² is hydrogen or T³, T³ issubstituted or unsubstituted C₁ -C₆ -alkyl, C₅ -C₇ -cycloalkyl, C₃ -C₆-alkenyl or phenyl, T⁴ and T⁵ are each, independently of the other,hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, benzyloxy, halogen, C₁-C₄ -alkylsulfonylamino, C₁ -C₄ -dialkylaminosulfonylamino, C₁ -C₄-alkoxycarbonylamino, substituted or unsubstituted benzoylamino or C₁-C₆ -alkanoylamino, T⁶ is cyano, nitro, acetyl, carbamoyl, C₁ -C₄ -mono-or -dialkylcarbamoyl, C₁ -C₄ -alkoxycarbonyl or C₁ -C₄-alkoxyethoxycarbonyl and T⁷ is unsubstituted or cyano-, C₁ -C₄-alkoxycarbonyl- or phenyl-substituted C₁ -C₁₀ -alkyl, phenyl, halogen,nitro, unsubstituted or C₁ -C₄ -alkoxy-substituted C₁ -C₁₀ -alkoxy,phenoxy, benzyloxy, C₁ -C₄ -alkylthio, phenylthio, C₁ -C₄ -mono- ordialkylamino, C₁ -C₅ -alkanoylamino or C₁ -C₄ -alkoxycarbonyl.

In a substituted C₁ -C₈ -alkyl B², possible substituents are chlorine,bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, substituted or unsubstitutedphenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkanoyloxy-C₁ -C₄-alkoxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- orp-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxy-C₁ -C₈-alkanoyloxy, phenoxy-C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁-C₈ -alkoxy-C₁ -C₈ -alkoxycarbonyloxy, benzyloxycarbonyloxy,phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈-alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy,phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxy-C₁ -C₈-alkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄-alkoxy and phenylethoxycarbonyl.

In a substituted C₅ -C₇ -cycloalkyl B², possible substituents are C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₂ -C₄ -hydroxyalkyl and hydroxyl.

An acyl B² is for the purposes of the present invention substituted orunsubstituted benzoyl, substituted or unsubstituted phenylsulfonyl,unsubstituted or phenyl-substituted C₁ -C₁₀ -alkanoyl or C₁ -C₆-alkylsulfonyl.

Specific examples of B² are: ##STR5##

Specific examples of T¹ are hydrogen, methyl, ethyl, propyl, butyl,benzyl, phenethyl, phenyl, o-, m- or p-tolyl and o-, m- orp-chlorophenyl.

In a substituted C₁ -C₆ -alkyl T³, possible substituents are chlorine,bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, phenyl, C₁-C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- orp-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxy-C₁ -C₈-alkanoyloxy, phenoxy-C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁-C₈ -alkoxy-C₁ -C₈ -alkoxycarbonyloxy, benzyloxycarbonyloxy,phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈-alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy,phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxy-C₁ -C₈-alkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄-alkoxy and phenethyloxycarbonyl.

Specific examples of T³ are methyl, ethyl, propyl, butyl, pentyl, hexyl,allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl,2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl,2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl,2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl,2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl,2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl,2-butyryloxyethyl, 2-isobutyryloxyethyl,2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl,2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl,2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl,2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl,2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl,2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl,2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl,2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl,2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl,2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl,2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl,2-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl,2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl,2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonyloxyethyl,2-benzoyloxyethyl, cyclopentyl, cyclohexyl, cycloheptyl, benzyl,phenylethyl and phenyl.

T⁴ and T⁵ are for example hydrogen, methyl, ethyl, propyl, bromine,chlorine, methoxy, ethoxy, phenoxy, benzyloxy, methylsulfonylamino,ethylsulfonylamino, isopropylsulfonylamino, butylsulfonylamino,dimethylaminosulfonylamino, diethylaminosulfonylamino,methoxycarbonylamino, ethoxycarbonylamino, propoxycarbonylamino,isobutoxycarbonylamino, formylamino, acetylamino, propionylamino,butyrylamino, pentanoylamino, hexanoylamino, benzoylamino,4-methylbenzoylamino, 4-chlorobenzoylamino or 2-methoxybenzoylamino.

T⁶ can be for example, in addition to those mentioned above, carbamoyl,methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl,methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i- orsecbutoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- ori-propoxyethoxycarbonyl or n-, i- or secbutoxyethoxycarbonyl.

Examples of T⁷ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl,nonyl, decyl, cyanomethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl,benzyl, phenylethyl, phenyl, chlorine, bromine, nitro, methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, hexyloxy, heptyloxy,2-ethylhexyloxy, nonyloxy, decyloxy, 2-methoxyethoxy, 2-ethoxyethoxy,2-propoxyethoxy, 2-butoxyethoxy, phenoxy, benzyloxy, methylthio,ethylthio, propylthio, butylthio, isobutylthio, sec-butylthio,phenylthio, methylamino, dimethylamino, ethylamino, diethylamino,propylamino, dipropylamino, isopropylamino, diisopropylamino,butylamino, dibutylamino, methylethylamino, formylamino, acetylamino,propionylamino, butyrylamino, pentanoylamino, methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl,isobutoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl.

Particular preference is given to thiophene-containing azo dyes of theformula I where R is C₁ -C₈ -alkyl or C₃ -C₅ -alkenyl, X is hydrogen,chlorine, bromine, C₁ -C₄ -alkoxy, phenylthio, phenylsulfonyl, C₁ -C₄-alkyl or phenyl, Y is cyano or CO--Z where Z is C₁ -C₄ -alkoxy, and Kis the radical of a coupling component of the aniline, pyridine,thiophene, thiazole or aminopyrazole series. These coupling componentsconform to the formula II, III, VI, VII, VIII or IX.

The novel dyes of the formula I are suitable for dyeing fiber material,in particular polyesters, nylons, cellulose esters or blend fabrics ofpolyesters and cellulose fibers. On these fibers, they produce dyeingsin yellow to greenish blue shades which, in general, have good to verygood fastness properties, in particular on polyesters.

Given a suitable constitution, the dyes are dischargeable under reducingand/or under alkaline and reducing conditions in a conventional manneras described in GB-A-1,543,724 and GB-A-2,071,707.

To prepare a compound of the formula I, a diazonium compound of an amineof the formula XI ##STR6## where R, X and Y each have the abovmentionedmeanings, can be reacted in a conventional manner with a couplingcomponent of the formula HK.

An amine of the formula XI is obtained by reacting a compound of theformula XII ##STR7## where X and Y each have the abovementionedmeanings, with an appropriate hydroxylamine ether in a conventionalmanner. The preparation of hydroxylamine ethers is known and isdescribed for example in Houben-Weyl, "Methoden der organischen Chemie",volume 10/1, page 1181 et seq., (1971).

Further details of the preparation can be found in the Examples, whichare intended to illustrate the invention in more detail. In theExamples, percentages are by weight, unless otherwise stated.

EXAMPLE 1 ##STR8##

37.3 g of 2-amino-4-chloro-3-cyano-5-formylthiophene were heatedtogether with 250 ml of glacial acetic acid, 26.8 g of 50% strengthaqueous O-ethylhydroxylamine and 10 drops of 85% strength sulfuric acidunder reflux for 1.5 hours. After cooling down, the light brown dye wasfiltered off with suction, washed with 50 ml of glacial acetic and 1,000ml of water and dried at 60° C. under reduced pressure to give 37.6 g(82% of theory) of2-amino-4-chloro-3-cyano-5-(O-ethylaldoximino)thiophene in the form oflight brown crystals. A sample recrystallized from ethanol had a meltingpoint of 221°-223° C. and the following analytical values: C₈ H₈ ClN₃ OS(229.5)

calculated: C 41.83 H 3.49 Cl 15.47 N 18.30 O 6.97 S 13.94%. found: C41.7 H 3.4 Cl 15.9 N 17.9 O 7.3 S 13.8%.

IR and ¹ H-NMR spectra are in conformity with the structure.

Table 1 gives 2-amino-5-aldoximinothiophenes of the formula ##STR9##which are obtained in a similar manner.

                  TABLE 1                                                         ______________________________________                                         ##STR10##                                                                    Ex. No.   R             X         Y                                           ______________________________________                                        2         CH.sub.3      Cl        CN                                          3         C.sub.4 H.sub.9                                                                             Cl        CN                                          4         CH.sub.2 C.sub.6 H.sub.5                                                                    Cl        CN                                          5         C.sub.2 H.sub.5                                                                             SC.sub.6 H.sub.5                                                                        CN                                          6         C.sub.2 H.sub.5                                                                             SO.sub.2 C.sub.6 H.sub.5                                                                CN                                          7         C.sub.4 H.sub.9                                                                             OC.sub.2 H.sub.5                                                                        CN                                          8         i-C.sub.3 H.sub.7                                                                           Br        CN                                          9         CH.sub.2 CHCH.sub.2                                                                         Cl        CN                                          10        C.sub.2 H.sub.5                                                                             Cl        CO.sub.2 C.sub.2 H.sub.5                    11        C.sub.3 H.sub.7                                                                             H         CN                                          12        CH.sub.2 C.sub.6 H.sub.5                                                                    CH.sub.3  CN                                          13        CH.sub.3      C.sub.6 H.sub.5                                                                         CN                                          ______________________________________                                    

EXAMPLE 14

5.7 g of 2-amino-4-chloro-3-cyano-5-(O-ethylaldoximino)thiophene (seeExample 1) were suspended in 40 ml of of 3:1 glacial aceticacid/propionic acid. 8.3 g of 40% strength nitrosyl sulfuric acid wereslowly added at from 0° to 5° C. After stirring for two hours at from 0°to 5° C. this diazonium salt solution was added dropwise to 5.9 g of3-(N,N-diethylamino)-1-acetanilide in 100 ml of water, 20 ml ofhydrochloric acid, 0.5 g of sulfamic acid and 125 g of ice. The dyesuspension was stirred at from 0° to 5° C. for 4 hours, and the dye ofthe formula ##STR11## was then filtered off with suction, washed withwater until neutral and dried. Yield: 9.6 g. The dye dyes polyesterfiber material in blue shades having good fastness properties. λ max(CH₂ Cl₂): 580 nm.

EXAMPLE 15

Example 14 was repeated, except that the coupling component3-(N,N-diethylamino)-1-acetanilide was replaced by3-(N,N-diethylamino)-1-methoxyacetanilide, affording 9.8 g of the dye ofthe formula ##STR12## which dyes polyester fiber material in fast, blueshades. λ max (CH₂ Cl₂): 588 nm.

Table 2 lists dyes of the formula ##STR13## which are obtained in asimilar manner.

    __________________________________________________________________________    Ex.                                          Hue on                           No.                                                                              R    X Y    T.sup.5   T.sup.4                                                                           T.sup.3 T.sup.2 PES                              __________________________________________________________________________    18 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   CH.sub.3  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       reddish                                                                       blue                             17 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   CH.sub.3  H   C.sub.4 H.sub.9                                                                       C.sub.4 H.sub.9                                                                       reddish                                                                       blue                             18 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.2 Cl                                                                         H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             19 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOC.sub.2 H.sub.5                                                                     H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             20 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.4 H.sub.9                                                                       C.sub.4 H.sub.9                                                                       blue                             21 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       greenish                                                                      blue                             22 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            OC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       greenish                                                                      blue                             23 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            OCH.sub.3                                                                         C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           greenish                                                                      blue                             24 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            OCH.sub.3                                                                         C.sub.2 H.sub.4 CN                                                                    CH.sub.2 CH═CH.sub.2                                                              greenish                                                                      blue                             25 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.5                                                                       blue                             26 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                             blue                             27 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.4 H.sub.8 OCOCH.sub.3                                                           C.sub.4 H.sub.8 OCOCH.sub.3                                                           blue                             28 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   CH.sub.2 CH═CH.sub.2                                                              CH.sub.2 CH═CH.sub.2                                                              blue                             29 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.2 CN                                                                         H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             30 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub. 2 C.sub.6 H.sub.5                                                           H   n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                     blue                             31 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   CH.sub.3  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OH                                                                    reddish                                                                       blue                             32 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   CH.sub.3  H   C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 OH                                                                    bluish                                                                        violet                           33 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           reddish                                                                       blue                             34 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   CH.sub.3  OCH.sub.3                                                                         C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           blue                             35 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   H         H   C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.5                                                                       bluish                                                                        violet                           36 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHSO.sub.2 CH.sub.3                                                                     H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             37 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOC.sub.2 H.sub.5                                                                     H   C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 OH                                                                    blue                             38 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   H         OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             39 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   CH.sub.3  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 CN                                                                    bluish                                                                        violet                           40 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOOC.sub.2 H.sub.5                                                                    H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OH                                                                    reddish                                                                       blue                             41 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   H         OCH.sub.3                                                                         C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           reddish                                                                       blue                             42 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH(CH.sub.3).sub.2                                                                  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             43 C.sub.2 H.sub.5                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.4 CN                                                                    C.sub.2 H.sub.5                                                                       reddish                                                                       blue                             44 C.sub.2 H.sub.5                                                                    Cl                                                                              CO.sub.2 C.sub.2 H.sub.5                                                           NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       reddish                                                                       blue                             45 C.sub.2 H.sub.5                                                                    Cl                                                                              CO.sub.2 C.sub. 2 H.sub.5                                                          NHCOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                     reddish                                                                       blue                             46 C.sub.2 H.sub.5                                                                    Cl                                                                              CO.sub.2 C.sub.2 H.sub.5                                                           NHCOCH.sub.2 OCH.sub.3                                                                  H   C.sub.2 H.sub.4 OCH.sub.3                                                             C.sub.2 H.sub.4 OCH.sub.3                                                             reddish                                                                       blue                             47 C.sub.2 H.sub.5                                                                    Cl                                                                              CO.sub.2 C.sub.2 H.sub.5                                                           NHCOCH.sub.3                                                                            OCH.sub.3                                                                         C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           blue                             48 C.sub.2 H.sub.5                                                                    Cl                                                                              CO.sub.2 C.sub.2 H.sub.5                                                           CH.sub.3  H   C.sub.2 H.sub.4 CN                                                                    C.sub.2 H.sub.5                                                                       violet                           49 C.sub.2 H.sub.5                                                                    Cl                                                                              CO.sub.2 C.sub.2 H.sub.5                                                           H         H   C.sub.2 H.sub.4 CN                                                                    C.sub.2 H.sub.4 OCOCH.sub.3                                                           violet                           50 C.sub.2 H.sub.5                                                                    Cl                                                                              CO.sub.2 CH.sub.3                                                                  NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             51 C.sub.4 H.sub.9                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   n-C.sub.4 H.sub.9                                                                     n-C.sub.4 H.sub.9                                                                     blue                             52 C.sub.4 H.sub.9                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 OH                                                                    reddish                                                                       blue                             53 C.sub.4 H.sub.9                                                                    Cl                                                                              CN   NHCOCH.sub.2 OC.sub.6 H.sub.5                                                           H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             54 C.sub.4 H.sub.9                                                                    Cl                                                                              CN   CH.sub.3  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       bluish                                                                        violet                           55 C.sub.4 H.sub.9                                                                    Cl                                                                              CN   H         H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       violet                           56 C.sub.4 H.sub.9                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             57 C.sub.4 H.sub.9                                                                    Cl                                                                              CN   NHCOCH.sub.3                                                                            OCH.sub.3                                                                         C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           greenish                                                                      blue                             58 C.sub.3 H.sub.7                                                                    Br                                                                              CN   NHCOCH.sub.3                                                                            H   n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                     blue                             59 C.sub.3 H.sub.7                                                                    Br                                                                              CN   CH.sub.3  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 CN                                                                    violet                           60 C.sub.4 H.sub.9                                                                    Cl                                                                              CN   CH.sub.3  OCH.sub.3                                                                         C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           blue                             61 CH.sub.3                                                                           (1)                                                                             CN   CH.sub.3  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OH                                                                    reddish                          62 CH.sub.2 C.sub.6 H.sub.5                                                           (2)                                                                             CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       reddish                                                                       blue                             63 CH.sub.2 C.sub.6 H.sub.5                                                           (2)                                                                             CN   CH.sub.3  H   C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 OH                                                                    bluish                                                                        violet                           64 CH.sub.2 C.sub.6 H.sub.5                                                           (2)                                                                             CN   CH.sub.3  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 CN                                                                    violet                           65 C.sub.2 H.sub.5                                                                    (3)                                                                             CN   NHCOCH.sub.3                                                                            H   C.sub.4 H.sub.9                                                                       C.sub.4 H.sub.9                                                                       blue                             66 C.sub.2 H.sub.5                                                                    (3)                                                                             CN   NHCOC.sub.2 H.sub.5                                                                     H   C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           reddish                                                                       blue                             67 C.sub.2 H.sub.5                                                                    (3)                                                                             CN   NHCOCH.sub.2 OCH.sub.3                                                                  H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             68 C.sub.2 H.sub.5                                                                    (3)                                                                             CN   H         H   C.sub.2 H.sub.4 CN                                                                    C.sub.2 H.sub.5                                                                       violet                           69 C.sub.2 H.sub.5                                                                    (4)                                                                             CN   CH.sub.3  H   C.sub.2 H.sub.4 CN                                                                    C.sub.2 H.sub.5                                                                       violet                           70 C.sub.2 H.sub.5                                                                    (4)                                                                             CN   NHCOCH.sub.3                                                                            OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       greenish                                                                      blue                             71 C.sub.2 H.sub.5                                                                    (4)                                                                             CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       blue                             72 C.sub.2 H.sub.5                                                                    (4)                                                                             CN   NHCOC.sub.2 H.sub.5                                                                     H   C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 OH                                                                    blue                             73 C.sub.2 H.sub.5                                                                    (4)                                                                             CN   NHCOCH.sub.3                                                                            H   C.sub.2 H.sub.4 CN                                                                    C.sub.2 H.sub.5                                                                       reddish                                                                       blue                             74 C.sub.4 H.sub.9                                                                    (5)                                                                             CN   NHCOCH.sub.3                                                                            H   C.sub.3 H.sub.7                                                                       C.sub.3 H.sub.7                                                                       blue                             75 C.sub.4 H.sub.9                                                                    (5)                                                                             CN   NHCOCH.sub.3                                                                            OC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CN                                                                    CH.sub.2 CH═CH.sub.2                                                              greenish                                                                      blue                             76 C.sub.4 H.sub.9                                                                    (5)                                                                             CN   NHCOCH.sub.3                                                                            H   CH.sub.2 CH═CH.sub.2                                                              CH.sub.2 CH═CH.sub.2                                                              reddish                          77 C.sub.4 H.sub.9                                                                    (5)                                                                             CN   NHCOCH.sub.2 OCH.sub.3                                                                  H   C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                           reddish                                                                       blue                             78 C.sub.4 H.sub.9                                                                    (5)                                                                             CN   NHCOCH.sub.2 Cl                                                                         H   C.sub.4 H.sub.9                                                                       C.sub.4 H.sub.9                                                                       blue                             79 C.sub.4 H.sub.9                                                                    (5)                                                                             CN   CH.sub.3  H   C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.5                                                                       bluish                                                                        violet                           80 (6)  Cl                                                                              CN   NHCOCH.sub.3                                                                            H   C.sub.4 H.sub.9                                                                       C.sub.4 H.sub.9                                                                       blue                             __________________________________________________________________________     (1) = C.sub.6 H.sub.5                                                         (2) = CH.sub.3                                                                (3) = SC.sub.6 H.sub.5                                                        (4) = SO.sub.2 C.sub.6 H.sub.5                                                (5) = OC.sub.2 H.sub.5                                                        (6) = CH.sub.2 CH═CH.sub.2                                           

The method of Example 15 is also employed to obtain the dyes of theformula ##STR14## listed in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Ex. No.                                                                             K                         Hue on PES                                    __________________________________________________________________________    81                                                                                   ##STR15##                blue                                          82                                                                                   ##STR16##                blue                                          83                                                                                   ##STR17##                blue                                          84                                                                                   ##STR18##                blue                                          85                                                                                   ##STR19##                blue                                          86                                                                                   ##STR20##                blue                                          87                                                                                   ##STR21##                blue                                          88                                                                                   ##STR22##                blue                                          89                                                                                   ##STR23##                blue                                          90                                                                                   ##STR24##                blue                                          91                                                                                   ##STR25##                blue                                          92                                                                                   ##STR26##                blue                                          93                                                                                   ##STR27##                reddish violet                                94                                                                                   ##STR28##                reddish violet                                95                                                                                   ##STR29##                violet                                        96                                                                                   ##STR30##                reddish violet                                __________________________________________________________________________

We claim:
 1. A thiophene-containing azo dye of the formula ##STR31##where R is C₁ -C₁₂ alkyl or C₁ -C₂ alkyl substituted by chlorine,bromine, C₁ -C₄ -alkoxy, phenyl or phenoxy, C₃ -C₆ alkenyl or C₃ -C₆alkenyl substituted by chlorine, bromine, C₁ -C₄ -alkoxy, phenyl orphenoxy, phenyl or phenyl substituted by halogen, C₁ -C₄ -alkyl or C₁-C₄ -alkoxy, X is hydrogen, halogen, hydroxyl, C₁ -C₈ alkoxy, C₁ -C₈-alkoxy substituted by phenyl, C₅ -C₇ -cycloalkoxy, phenoxy, phenoxysubstituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, mercapto,alkylthio, alkylthio substituted by hydroxyl-, C₁ -C₄ -alkoxycarbonyl-or phenyl, C₅ -C₇ -cycloalkylthio, phenylthio, phenylthio substituted byhalogen, C₁ -C₄ -alkyl or C₁ -C₈ alkoxy, C₁ -C₄ -alkylsulfonyl,phenylsulfonyl, phenylsulfonyl substituted by halogen, C₁ -C₄ -alkyl orC₁ -C₄ alkoxy, C₁ -C₈ -alkyl, phenyl substituted by halogen, C.sub. 1-C₄ -alkyl or C₁ -C₄ -alkoxy; Y is cyano, nitro, C₁ -C₁₀ -alkanoyl,benzoyl, benzoyl substituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, phenylsulfonylsubstituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, or CO--Z whereZ is hydroxyl, C₁ -C₈ alkoxy, C₁ -C₈ alkoxy substituted by hydroxyl- orC₁ -C₄ -alkoxy, phenoxy, phenoxy substituted by halogen, C₁ -C₄ -alkylor C₁ -C₄ -alkoxy, amino, C₁ -C₈ -mono- or dialkylamino, pyrrolidino,piperidino, morpholino or N-(C₁ -C₄ -alkyl)piperazino and K is theradical of a coupling component of the formulae II to X: ##STR32## whereB¹ is hydrogen or B², B² is C₁ -C₈ alkyl, C₁ -C₈ alkyl substituted bychlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano,carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkanoyloxy-C₁ -C₄ -alkoxy, C₁-C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy,o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxy-C₁ -C₈ -alkanoyloxy,phenoxy-C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈-alkoxy-C₁ -C₈ -alkoxycarbonyloxy, benzyloxycarbonyloxy,phenethoxycarbonyloxy, phenoxyethoxy-carbonyloxy, C₁ -C₈-alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy,phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxy-C₁ -C₈-alkoxycarbonyl, phenoxy-carbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄-alkoxy or phenylethoxycarbonyl, C₅ -C₇ cycloalkyl, C₅ -C₇ cycloalkylsubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₂ -C₄ -hydroxy-alkyl orhydroxyl, phenyl, C₃ -C₆ -alkenyl or acyl, T¹ is hydrogen, C₁ -C₄ alkyl,C₁ -C₄ alkyl substituted by phenyl, phenyl, or phenyl substituted byhalogen or alkyl; T² is hydrogen or T³, T³ is C₁ -C₆ alkyl, C₁ -C₆ alkylsubstituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy,cyano, carboxyl, phenyl C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄-alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- orp-chlorobenzoyloxy, C₁ -C₈ -alkoxy-C₁ -C₈ -alkanoyloxy, phenoxy-C₁ -C₈-alkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxy-C₁ -C₈-alkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy,phenoxyethoxy-carbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy,cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈-alkoxycarbonyl, C₁ -C.sub. 8 -alkoxy-C₁ -C₈ -alkoxycarbonyl,phenoxy-carbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy orphenylethoxycarbonyl, C₅ -C₇ -cycloalkyl, C₃ -C₆ -alkenyl or phenyl, T⁴and T⁵ are each, independently of the other, hydrogen, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, phenoxy, benzyloxy, halogen, C₁ -C₄ -alkyl-sulfonylamino,C₁ -C₄ -dialkylaminosulfonylamino, C₁ -C₄ -alkoxycarbonylamino,benzoylamino or C₁ -C₆ -alkanoylamino, T⁶ is cyano, nitro, acetyl,carbamoyl, C₁ -C₄ -mono- or -dialkylcarbamoyl, C₁ -C₄ -alkoxycarbonyl orC₁ -C₄ -alkoxyethoxycarbonyl; and T⁷ is C₁ -C₁₀ alkyl, C₁ -C₁₀ alkylsubstituted by cyano-, C₁ -C₄ -alkoxycarbonyl- or phenyl, phenyl,halogen nitro, C₁ -C₁₀ alkoxy, C₁ -C₁₀ -alkoxy substituted by C₁ -C₄alkoxy, phenoxy, benzyloxy, C₁ -C₄ -alkylthio, phenylthio, C₁ -C₄ -mono-or dialkylamino, C₁ -C₅ -alkanoylamino or C₁ -C₄ -alkoxycarbonyl.
 2. Athiophene-containing azo dye as claimed in claim 1, wherein R is C₁ -C₈alkyl or C₃ -C₅ -alkenyl, X is hydrogen, chlorine, bromine, C₁ -C₄-alkoxy, phenyl-thio, phenylsulfonyl, C₁ -C₄ -alkyl or phenyl, Y iscyano or CO--Z where Z is C₁ -C₄ -alkoxy.